DE2041023A1 - Process for coloring polymeric materials - Google Patents

Description

MTENTAHWXUI DRYING. H. FfNCKB PIPL-IMG. H BOHi Dlt'L. ING. S. STAEGER MÖNCHEN 5 MOLLERSTR. 31

1 AUG. 1970

Imperial Chemical Industries Xdnited Europe UKia

Process for dyeing polymeric materielies

You Brfinduag "relates to an improved Verjf Amm sum dyeing iron polymers

Se is fcetettt ;, polyiierfi Mutrieliea- «» Β ™ ia i7oa 'TOB.'ftxttiiett: d «dttreh m farbea.« Tmee ei · nit

109009/2090

F erbet open solutions in organic solvents be treated. 80 Is it known that textiles see B. in a continuous process su drink or su print old solutions from dyes in an organic solvent or Solvent gft & iJteh if necessary with Yerdlokungsmltteln, if necessary, remove a substantial part of the excess dye liquor and »Ofelle« send dl · coloring bsw. the pressure by a Fix subsequent heat treatment see below. Si · choice The dye as a solvent for such processes is, however, well understood, since the dye is used in Normal temperature and a little more in the solvent soluble selA nut and you rarely get enough Solubility for more than weak or medium rerbtoatiefen finds.

8oll «n especially non-flammable, chlorinated« or fluorinated · aliphatic * hydrocarbon · as Solvents are used, so have many available dyes have such a low solubility ia eolefeen Lö «umgemitt« ln that just pale ftxbto & e erslelt «earth. Medium deep kings in a «· soloben Terftalntn # etdnroli ~ whoever reaches ^ «»

- 3 KtlCt / 2030

to increase the solubility of the dye will. Si · use of such süätslieher However, solvents often lead to one or more of the following disadvantages: increased effort, Risk of explosion, difficult recovery of solvents, impairment of fiber properties

It is also known to make textile fabrics from solutions Clay dyes in organic solvents Exhaustion methods operated by paragraphs see below To dye. In this case, however, is the degree of exhaustion mostly very bad, even if the dye and the solvent are chosen so that the Minimal solubility of the dye is required has the necessary solubility for this staining method. Exhaustion can be reduced by gradually adding a susatlichen solvent during the dyeing process to reduce the solubility of the Dye can be increased. This way of working is However, it is cumbersome and can be done with the solvents that are used, such as the non-flammable ones halogenated hydrocarbons are not terreal.

109809/2030

The methods according to the invention can do a lot various dyes from organic solvents Applied in batches or continuously bsw. can be printed on, with level, real color tones arise which, if desired, can be obtained in deep shades.

According to the invention there is a method of sun dyeing ▼ on polymeric materials proposed that the polymeric material with a stable Deflocculated dispersion of a small particle size dye in an organic liquid treated so that the organic liquid is then removed and that the polymeric material during or after the treatment with the dispersion is heated.

Has the phrase "coloring polymeric materials" should be understood that the dyes incorporated into the polymeric material or on the Material are adsorbed. This term includes the mechanical binding of dyes on the Surface of the polymer material by means of binding material, like B.B. in pigment printing processes.

109809/2030

■ - 5 -

The polymeric materials have any suitable shape with a large surface area relative to the Volume, e.g. the shape of threads, fibers, textile fabrics from such threads or fibers, films, tapes or powders. As examples of polymers Materials can be mentioned as follows: cellulose » containing fibers from e.g. cotton, flax, hemp, Jute, sisal and ramie, regenerated cellulosic © fibers from e.g. viscose and copper rayon, Cellulose ester fibers from e.g. cellulose acetate and -triacetate, natural protein fiber from e.g. wool, Silk and mohair wool, regenerated protein ©, synthetic polyamides such as Ify-lon 66 and Ifylon and modified polyamides, polyesters, see B. Polyethylene » terephthalate, and modified polyester, polyacrylic «» nitrile and modified polyacrylonitriles, polyurethanes and materials such as leather and hides.

about the term "stable deflocculated dispersion" a dispersion should be understood in which a negligibly small proportion of the approach® » of the particles of the dispersion phase to one another Adhaealon between the particles leading Ic.

, -die-no BbaMLeiionbfLdokfcdn- BIa-

, taxes very similar

Coloration, even if the particle size is very fine is.

-great
The particles of the dye should be below 25 μ,

»Ugeweiea below 10 μ» II®gen »i.e.» that the larger proportion of the particles form an equivalent circle, diameters below the specified Grense have aoll, * if a diluted i? rob® of the dispersion is observed with the microscope.

Organic liquid can be any organic material which is partially liquid at the color temperature, which dissolves the polymeric material / licat or whose cheaisct & e Zuaai »§aaitt% ung odor physical form undesirable Ibaalafluesu, while the» la has such limited loatiagsYeiisgen for the dye, that an iterative part of the dye is in the undissolved state at least as far as the dyeing profieases.

As examples of organic liquids that can be used, assuming that they are suitable for a particular polymeric material and dye, kiuui Ban mention the following: alcohols such as flihanol, n- and lao-butanol, and fupfur / l «and tetrahydrofurfuryl alcohol,

Ketones such as cyclohexanone, esters such as butyl acetate, Xther such as Bioxane and XthyleneglykolBonomethyl- and -monoathylether, hydrocarbons such as testbene and IyIöl, and halogenated hydrocarbons such as Chlorbensol and 1,1,2-TrIcIiIOr-I ^, 2-trifluoroethane. The preferred organic liquids are hydrocarbons and halogenated hydrocarbons. In particular, the following are preferred because they la general allow easy recovery ( and are non-flammable: lower aliphatic «halogenated hydrocarbons, like c.B. Chloroform, carbon tetrachloride, 1,1,1-trichloroethane, trichlorethylene, Dibroaäthyleh and ror all tetrachlorethylene (PerchlorethyleneV?

Hiachungen from these liquids sf4s ° Hiachungen of organic substances which under the £ _»u, L, S; dee puigen method according to the invention are liquid, can also be used. The presence of τοη inorganic liquids, especially water, can be accepted as long as a substantial proportion of the dye aa at the beginning of the dyeing process is undissolved in the organic liquid and the inorganic liquids do not affect the polymeric material.

10980972030

BATH ORIGINAL

All dyes are known to all organic dyes or fleas if they have the necessary limited solubility Use in the organic liquid. All examples of this know especially disperse dyes and mention water-soluble dyes. These dyes can be any known dye series belong to; you can s.B. Diarylmethane, triarylaethane, Ian then, AeIn, Oxa »in-, or Thhlasin dyes and in particular aso-, anthraehinone, vitro, Phthalocyanine, phthalocyanine, styryl, laphthoperinone, oleophthalone or 5-amino-8-hydroxy-1,4-naphthophthalone be dyes.

(Dead water-soluble dyes are in particular Baische dyes, i.e. dyes old cationic group, as well as the so-called acid and direct dyes combined.

Honoaso and Oieaso dyes are recognized aso dyes and their affiliated rate. Ale Beleplele for these associated azo dyes can aea eolohe mention, let them have a copper », Ohroa- or Kobaltatoa to a molecule of a mono-arbetoffe is bound, or la which a chromium or xobaltatoei «n swel molecules τοη resemble or rereohledenen Honoaso dye is bound. Such

109809/2030

Aesallized dyes can optionally contain water-solubilizing sulfonic acid or carboxylic acid groups

These dyes can all sit fibers reactive Contain groups, i.e. groups that have a coralent effect on fibers or other polymeric substrates Ability to form bonds. ·

The dyes should be chosen in such a way that they have a bit of staining in terms of the polymeric material to be colored · X * are disperse dyes generally suitable for colors of polyesters, cellulose esters, Hyloa and modified polyacrylonitrile? Acid dyes, direct dyes and reactive dyes sub dyeing of cellulosic materials and natural and synthetic polyamides j the Ä

cationic dyes; dyeing of synthetic polyamides and modified polyacrylonitriles. When using mixtures of different polymeric materials, sB _e polyester Bawsawoll or Folyeeter Wool Geiiengen, in de "V # rf" Uran.mim a corresponding G® "IEEA. τοη dye®a mm- '. Coloring of the Einselnan So ^ ponenteii of the 6t »eag · .-. .-. applied wtMta ». Examples of f «rbutofft ta? ο · »« ν # ι? ι »ω. · ιδ» »ιιι-ΟΛ ··· ιι niiil'ill Col«? ΙηΙ ζ ₉ . - -. - -

■ ¹ Y -Ö SQ 0 S / 2 0 3 0

2nd edition and listed maoh carriers

The entflookte dispersion fir da * "learn to de * Irfiadaag can be prepared by the · the fsrbstoff la presence of the organic liquid and elnea Sntflookimgamittel" vat V * r ■ tldunc tob ZiniB-nhil 1 nn ^ s d ·· solid · ge-BBblea is · Bs 1st much aSglleh "a autodieperglerberee Pulrer" us of the dye-old of organleohen Hasslfjtolt la Oeerawart tob Elaea SntflookuagSBlttsl sa Terrähreai or the dye kaaa la elaejeepalt the oraaBlsoae Fliieelekelt ^{v N} are Ladea • read wieeerlge flaspeasloa or Faete tob the dye is extracted from an organ-free wing, aad »was la presence of a fiitflookungaalttels or with subsequent addition of fertfloktmg · leaves.

The Aitflookaagaalttel for dl · Production of the Dleperelons are rorsugswelee Blndeetena partially ldslloh la the Organleohen FlÄeeigkelt. iXs examples ffbr Attflookongsalttel kaaa aan the following mention ι Bsljureas, which are the essential trmi tob basic ialno groups and Blndesten swel afaesstoffigrttppea as well as alndesteas swel alkyl- »

! «9809/2030

I · I ·

Alkenyl or alkapolyenyl group with each contain at least β carbon atoms like them in British Patent Application 4-1 058/69 are described, and the compounds of the formula

OHH

Ar- (CH-CEO CCCC-OH
η it

BR

where Ar is an aromatic group, η is 0 or 1 is, 2 to 5 B groups each hydrogen, methyl or ethyl and the remaining B group bsw the remaining B groups each alone or in the remaining combination H-O-C-H one represents solvatable chain-like component with at least 12 links bsw represent as they are in British Patent 1,106,261 are.

The amount of dye depends on τοη ».Β. the desired depth of shade and the tinting power as well as the dyeing ratio of the dye. In general However, an amount of dye of 0.2 to 5% by weight is sufficient based on the polymeric material, although more or less can be used.

The dependance on Kntflooktmgammittel is dependent on τοη the deflocculation effect of the agent in question

- 12 109809/2030

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.- 13 -

dried and heated to a temperature of 80 to 220 ⁰ C, for example.

Accordingly, the dispersion can be sprayed or printed onto the textile material. "

When cellulosic textile fabrics are active dyes according to the inventive method '

to be colored "this is how coloring" becomes in the present carried out by an alkaline agent. In this "trap used" to the alkaline agent also in the form of a stable dispersion in one organic liquid.

If necessary, further auxiliaries can be present, in particular auxiliaries which are soluble or dispersible in the organic liquid. At λ

Dispersions made after the printing or soldering process are applied, it is sometimes advantageous if thickeners, especially thickeners based on cellulose esters or polyvinyl alcohol can also be used.

The use of organic Ilüesigktltett » especially «halogenated» alifhatiicben lohlenw * »ser« toff # », al «flüeeif ·· Kedlua aaeiat *

at firbeproseesea a Belhe roa brings Yortellan ■ it provides dtt colors is done faster Ib lrschoprerfehren, «Ed for! Soldering process« lid dss

Textile goods lighter bcnetst "ad der larbatoff tessar wifmnn — iMt di · organlsebta Wisstsjnsltsn BSbsii • las aisdrlgsv · spssiftseM sausage sovit tlat Bitdviftvt TtydimstvBgskiiltt eis Vasasv, so Asss adsv · svitdga bsimasv, so Asss dsv sv Ultdmr- ▼ tyisjadsag wlrtsohaXtlieli wlsdtrttwoansn wsidta came * wodnMb dl · laser sttvkt * vszdsndstt §ttps $ tvtsjstitta oti the treatment of AbviUsum Ttratfitn. further is tust Ansanl vwt Vssea ^ «ad ▼ trftJhren la Aloht wUserlee * Hftdlt» darekfihrt that this fovsjsait ia gtti gettsi fillta alt dta

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181101/1630

Temperatures up to 100 ° C under reduced pressure Will get removed*.

Example 2

The procedure is as in Example 1, with the exception that instead of the dispersion of 1,5-dihydroxy-4, e-di (Bethylaaino) anthraquinone Dispersions of i-Hetfaylamino-4-ß-hydroxyethylaminoanthraquinone (OolorIndex Dlspereblau Br.3) and 1, ^ - dihydroxy-5, β-di (ß-hydroxyethylamino) anthraohinone (Oolor Index Dispereblau Br.7) can be used. The pieces of tissue are strongly colored.

The dispersions used are each prepared as follows

BIa Gealech from 10 parts of dye, 5 parts of the in _ in the manner described below Polyureas and 163 parts of perehloroethylene are processed in the ball mill for 16 hours, which results in a finely divided, well deflocculated dispersion.

The Polyharnatoff used is represented by the fact that a solution of 73.7 parts of a La Bendel obtained 40% solution (in. Butyl acetate) polymerize from a * (tonic from 2,4- and 2,6-

- 17 -

109809/2039

«F

< i

- 17 -

Tolylenediocyanate with 5,7 # xsoeyanatgrtppen and less than 0,5 # free foljlendiisoeyanat in 32 parts acetone gradually as a solution of 53,5 parts of a secondary fatty amine derived from soy and commercially available under the name ABKEEH 2B , in 118 parts of acetone at 50 Ms 55 ° 0 is added with stirring. The acetone is then distilled off at temperatures of up to 100 ° 0 under reduced Brück · -

Similar results are obtained if the above Polyurea in the manufacture of the dye

dispersions presented by the following people

Polyurea is replaced Its solution of 37 * 5 ropes one in trade «AlXt ~

borrowed 509 ^ solution. '(Sm Ithylaeetat) trau ^ k' ::.

poljaerisi®rt «a vi & mXmu from .SolyleadiiaoeyiHis ^ E. Bit- ^ ' ä .a iiieijpijpa BslTaesisAtioiABgsad «Al itit O ^ fl folyitaiiieoeyasiftt« ad 11 »2St leoeyaaa'bgiiiijEpcr · Ca 15tβ ftilem Icetoft« is £ allaSnlielia «5» a lianptsaelilietL OleylaeSa, 4ae i »laadel vafoor leae» ASHBBV O evaaltli ^ ii. is »in the 8? for sale

«O ■ 'he

OfBGlNAL INSPECTED

Stirring is indicated, followed by acetone bsi Teapermturen up to su 10O ° 0 under varied tea We distilled off pressure «.

Example 3

Un piece of tissue aas polyethylene terephthalate (6 Qevlehtsteile) is * IttH ^ ₉ e 1 Stead in Sinaa Qeaisch from 1.07 Tahaa used in Example 1 Dispersion Sound 1 ". 5 - Younger (" etlyls "ino) siithracainon and 195 Tsilsn" irchloräthjlen η fliedepwakt §efirbt. It creates a good, eleiphsrnssigs firbang des Qevebes. Will this Torfsas; vlederbolt, alt de "Hstersohied, that no Faljrharaatoff is used, this is how angloiofasüssies fsrbnag arises, because the dispersion is not flooct.

Hat! Hall! ■ well «, glMUImm & lW firbtmg will stach • stalten, wxäst the foretng 1» ®i Tenwadnsag «tear ^ Dispereioa from i

(Oolor ladtz fiol «tt fr.®}, dl · asjeh & mt D * retellun wtis · emia» Β · 1ΐφ1 # 1 2 fir Us lttffitsllinie

trtaUwn tflrd ^ mi®d «rhjoit'wlrd ·

liit Ck «v« tev4 »bk am · B» l7ltli7 _: liiBi ^ w «$ Mhii3.ft« (6

! ■ 09809/2030 .. op ^ nal inspected

t-

Gaunt parts) becomes · 1 StiiMea in. «Iaea Gesleea ecus 92 parts of Tesfcbensin and 0.78 parts of fellesi «lner ▼ whether 1

(160 ⁰ C) colored, E «« Gtet «iat # 1ώθ good,

The dispersion used is as follows shownί.

Sin Geaiaob from 10 Τ · 11 · & dye, f parts &% m according to Example 2 withe AUSEBB 28 d & rgeet «llte £ PoSjhametojrjr« tjnd 77 parts Sestbensiii is worked 16 hours in the · Κιΐ ($ «1» ϋΐϋ «Y, vodurob 9i & m finely divided _£ eiiffliiektt Di ^ pj? iiioa emteteht ...

Example 5

QewelMietück asm Bo2j £ ttiarl "Bt" 9 "plit! I" lftt a Qeaieeti au "10 part" id "7 Ib

1 ve, T * f * ndeten Disperaion vob i ^ Dited ^ Bdi

(a © tljylaMino) anthraefainon tmd 90 parts Perchlosv ethylene to the Klotsrerfehren. Sach des Drying and not in the event of a Daapfbehaäling for 2 1 »i 180 * 0 0Ä» r a HiseeiieliaBSlimg-.Ifir 1

Μ «atetiiW eiae .gut # ₉ glelc & Bessdg ©

1.fStiil2i.fi · OFItGINAtINSPECTED

20A1023

Correspondingly good, same colorings will be according to this procedure even when using the dye « Material dispersions, the vegetables Example 2 produced will get.

Example 6

The procedure is as in Example 5, using a mixture of 20 parts of a dispersion of 2,4-dinitro-4 ^l -hydroatydiphenylamine (Color Index Yellow Ir.1) and 80 parts of ferrochlorethylene, prepared in the Veiee described below. A good, even, washfast color is produced.

A mixture of 10 parts of dye, 1 part of the gsmass Example 2 from ABKZEH 28 shown poly « ureas and 163 parts of perchlorethylene is processed in the ball mill for 16 hours, whereby a finely divided, well deflocculated dispersion is produced.

Example 7

The procedure is as in Example 5, with a mixture of 10 parts of the one described below Way represented dispersion of 4,8-diamino-1,5 ~ dihydroxyanthraquinone and 93> Divide perchlorethylene is used and the heat treatment 2 minutes

109809/2030 " ²¹ "

I 4

«1 t

instead of 1 minute at 200 ° G · Thus the result is a good, even, washfast color.

The dispersion used in this case is obtained by dispersing, according to the procedure of Example 1, 4 _{t of} 8-Dia-1 _{t of} 5-dihydric acid, instead of Color Index Diaperablau Hr.26. i

Example 8

6 parts of piled tissue made of fiylon 66 are placed in a varnish bath, since 0.756 parts of a dispersion of sodium salt of i-amino-4-anilinoanthraquinone-S-sulfonic acid prepared in the manner described below, 0.2 part of Ieopropylaeinealees der Contains dodecylbeniolaulfoic acid and 192 parts of perchlorethylene · The dye bath is 1 hour long

aa Boiling point increases · Meanwhile, it is exhausted The dyebath almost completely contained the dye. There" Oewebe is then referred to as perchlorethylene washed and dried. So you get a deep blue one coloring.

The dispersion used is thereby produced daae 10 file dta ITatriusaalsee der 1-A »ino-4-anilinoanthraquinone-2-aulfoic acid, 5 file of the

... ■ - ■■ '■■■■■ - ■. ■ ". ■■■ ■ -» ■■ -

109808/2030

Polyureas and 163 parts of ferrochlorethylene 16 represented in the manner described below Hours in the ball mill.

The polyharnetoff used is represented by the fact that a solution of 29.8 parts of an ia commercially available 75 * solution (in ethyl acetate) of a mixture of tolylene diisocyanates and polyols old 14.1% of residual xocyanate groups in 16 parts of icetone gradually su one solution of 53.5 parts ABREDI * 0 is added with stirring 28 in 118 parts of acetone at 50 to 55, and the acetone is distilled off at temperatures up to 10O su ⁰ G under reduced 'pressure.

Example 9

_fc 6 parts aufgehäuftes tissue from lylon 66 are placed in a dye bath that 0.64 parts of a dispersion prepared in the manner described below catfish tob 1-AmiJK> -4-anilinoantbj: achInon-2-eulfosjture and 192 parts Berchloräthylen contains · The The dyebath is then kept at the boiling point for 1 hour. Then the fabric, which is dyed a light blue shade, is taken out, rinsed with perchlorethylene and dried.

- 23 101809/2030

ν 2Q41023

The dispersion used for this is produced by that a Geaiech from 10 parts of i-Aaino-4-anilino-anthraehinone-2-sulfoic acid, 5 parts of the IA Example 8 used polyureas and 163 parts Perchlorethylene is processed in the ball mill for 16 hours.

Example 10 . I.

A fabric made of a differentiated polyacrylonitrile, which is available under the trade name GOÜHTELLE, and a pile of fabric on top of ftylos 66 (Jewell 3 parts) are placed in a bath of paint containing 0.96 parts in a manner described below The dispersion produced and 192 parts of perchlorethylene contains «before the paint is carried out for 1 hour at boiling point. The fabrics, which are dyed in yellow shades, are then drained, rinsed with perchlorethylene and dried. i

The dispersion used here is prepared by making a mixture of 10 parts of the Fonel I dye, 5 parts of that in Example 8 used polyureas and 163 parts perchlorethylene Processed in the ball mill for 16 hours

109809/2030

Formally It

OT- CH

OE

GH -

4 ^; 0.5

6 f # tl «aufinuttee Ghbw · '!» mn *% loa 66 were introduced into fil fojrbefead, Ame 0.6 * parts-one in niter camouflaged totsotalii!>"jaezt Veise berge β te 11th ¹ WtM latri'tieetl" the 1 ~ (2 ^> -Sulfon ~ 5HBetbgrl-

0.2 felle dee Iec ^ roporla «l, o, i» eJ. »TB der Oodecylbensol- waä 192 part« Ftre & lor & thylen contains · Dae

iflf € Anna. Ifjag. · «« Receives "and 1 sttnid ·« ii held. Dme Qjiw · '!) «Is then, out-

β · »β · ίΐιιιΐΗι, nit Γ ji rcIiIni'ii I Ii ι J if ι, j ι ¹ II ι κι dried · · ιΐΐΐ ι · .1 Il ι *. 11 β Ilia J ι υ ι Ii 11) 1111 ΙI «ι ϊ ϊ ■ n 11 'in riming ·

Uli Λ ι ι ml «ι im n ¹ MiI η ILH i , n

ti κ ι ■ ι ι in 4 ι iini inulin . (Kl ι I Il ι

¹ I ¹ IiIi ι 11 lh I iiiiii n ¹¹ I up I 11 κι 11 in Il "Ί ¹ I ι ι

111 "IUJ ¹ I ₁ ι ¹ In

Il Hl 'I ¹ IhI ¹ Il Ii 1I ₁ IIiIl II, ■ II ¹ Il 1 II,,

ι .1 ΙιΊ ¹ , ΙιΙ'ι "" II ι

Deeohrebenen, shown from IBMEEH 2S. Polyureaβ in a burrow old stone filling is processed.

Example 12

10 files of a fabric made of polyethylene terephthalate are boiled for 1 hour in a mixture of 1.6 files of a dispersion of 1,4-BiS- ( ^{I 1} -ethyl-4'-hydrosypbenyla8o) bensol and 192 layers

Perchlorethylene colored. The tissue is then «it Rinsed and dried perchlorethylene. Ee arises

a glelohaässlger yellow shade «

The dye dispersion used was thereby made that a mixture of 10 skins of dye,

5 filing of the custom Example 2 from ABMEBBT 2S shown Polyureas and 145 furs perehlor-

Ethylene processed in the ball mill for 14 hours I

became, . ; ; - _; ^: '■■ ■■■■ "- ■■■ ^; ■

Example 13

6 skins of a GeweDes from Bolyäthylenterephthalat be au one hour boil (160 ⁰ O) festbensln file in a mixture of 48 and 0.6 skins of a dispersion of 2-M * tbjl-4- (di-ß-hydro3tyäthyla "ino) -2 · -Ehlor-4 • - (l ^ p-chlorathyleulfonaaldo) asobensol colored · This creates a smooth, deep texture

109809/2030 -26-

- 26 aoharla-red coloration.

Di · used · here · Iarbatoffdieperaion is · obtained by making a Qeniaoh of 10 parts Farbatoff, 5 parts the gamaaa Beiapi ·! 2 a «· IBHEEH 28 polyureas represented and 85 parts of Teatbens worked in 16 hours in the ball mill became.

free game 14

Έ9 vlxd worked as in Example 13, where ·! However, part of the 0.6 file of the dye diaper used there 0.96 parts of a Diaperalon τοη 2-Hethyl-4- (di-ß-hydroxyäth7la »ino) -4 ^l -nitroa * obeii« ol are used, whereby a smooth deep red · coloring is obtained.

The dyeing period was obtained as a result of the fact that an oea of 10 parts of dye _v 5 parts of the polyhara fabric produced from AUUSEI 2β and 145 parts of perchlorethylene are processed in the ball mill for 16 hours.

»Eiapiel 19

10 parts are piled up a tissue aua a> loa 66 Divide an hour of boiling into one ·· Oeniaoh ama 160

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109801/2030

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• Internal Veme treatment for 2 minutes at 20 ° 0 subject. Bae fabric is then made with perchlorethylene rinsed and finally dried. Ee a “uniform scarlet coloration with good fastness properties is obtained in each case.

The dye dispersion used was obtained by processing a mixture of 10 files of dye, 1 file of the polyureas shown in Example 2 from ABKESSK 2S, and 150 files of perchloric ethylane for 16 hours in the ball mill

Üan maintaining a gleic'hmlssige yellow coloring nasseehte when the above dye by the same amount 2-37dro3tj-5- »etbyl-4 '- (l2''- chloro-4 ^fl - (die-hydroxyethylamino) - 1 ^lf , 3 ^W »5" -tria * in-6 "-jla« ino) asobensol replaced.

Example 17

The procedure is as in Example 13, old the Ibvtielüuae, the next 1.6 file the there applied dye dispersion 1.6 files one Dispersion of 1,4-bis ~ (Y ^ hloi> »ß ~ hydiro2ypropyl ·» aaiiio) anthracElnoii uses wn * diin, wodureb · 1ιιβ gl "iota" will have an identical blue coloration. Will

109809/2030

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the staining process 1 hour in a closed vessel at 150 ° G and not 1 hour at the boil (121 ° O) carried out, this creates a deeper color «

The dye dispersion used was like prepared in Example 15 using the same amount of blue dye

Example 18

e bleached
I am a piece of fabric made from construction wool type "Indian Bead ^11" was processed according to the Klot "by a pleasure! Look

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olle

Dispersion of the disodium salt of 1- (Dichiortria »iaylasiino) -7-pheDyla» oe-naphthol-3 _t 6-di8ulfo8 acid 10 ropes

Dispersion of Hatrlumblearhonat 10 pelts

■ ■■ ■ ■ ■■■ -. ■ "-. ■■■■. ■■ '.- ■■ t.'. '.' . ■ "■■■ Berehlorethylene 80 file

100 horny

and anschliesfend swlsohen orphan · routed The fabric is then dried and subjected to steam treatment at 10O ⁰ fjminütigen C. Finally it is washed with a dilute aqueous soap solution at 100 ° 0.

The dyestuff dispersion is obtained _by processing a mixture of 10 parts of the dyestuff, 0.75 parts of the polyureas shown in ABHEBH 28 from ABHEBH 28 and 90 parts of ferrochlorethylene for 16 hours in the ball pit.

The bathlumbicarbonate dispersion is obtained by because a mixture of parts of Bateiumbioarbonat, Share the vegetable example β shown polyureas and 88 parts of perchlorethylene is processed in the ball mill for 16 hours.

Instead of the 10 part · the sodium bicarbonate dispersion are used in the implementation of the · Example · 18 10 parts a dispersion of sodium carbonate or 10 parts of a dispersion of latriumhTdxt & qrd used, wherein similar red camouflages can be obtained.

Di · dispersions of potassium carbonate and sodium hydroxide are produced analogously to latrium bicarbonate diepereion.

example

Ub piece of fabric made of bleached cotton type "Indian Bead" is made by the padding process • la temlsch from

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Faxbatoff dispersion Example 18

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example 15 16 file vegetables 36 , 4 fill 391 feil® 20th 365 _$ 4> file

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cyanobensthiasol-2 · ~ ylaeo) -N, N-di (β-acetoxyäthy 1) -aniline and 475 parts of ferrochlorethylene passed. The fabric is dried and then erhitst for 1 minute at 200 ⁰ C. The fabric is then rinsed in an evulsion, which consists of 10 parts of water, 10 parts of xoconut oil diethanolamide and 980 parts of Perohlorathylen, and then dried. This gives you a uniform red color, which is washable and really let against heat and dry heat treatments *

The dye dispersion was produced in that © in Geaiach from 100 parts of dye, 6.25 parts of certainly Example 1 illustrated polyureas and Share Perchloräthylon 16 hours in the ball processed became.

Its blue color is obtained when the dye used in this example has the same slope "2-Ae" tyla "ino-4 ~ { l ~ ß-methoxyethoxycarbonyl) -äthylamino) -5-» e thojcy-2 ·, * ' -dini tro-6'-chlorasobensol is replaced.

Example 21

A "locknit" fabric ame% lon 66 to u »u Hots- ▼ arfahren one by one Genieeb from 16.7 parts

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Dispersion of sodium from i-phenyi-3-eetnyl-

and 983 files Perch! orethylene and then »Headed wipe orphans · The tissue is dried and then a 7-minute Daapf treatment under a «

Subject to pressure of 1.4 atmospheres. The tissue will

then rinsed with water and dried. Consequently a yellow coloration is obtained which has good fastness

against nasal treatments. '

The dye diapersion was obtained in that a Grenisch from 10 parts of the dye, 1 part of the geaäss example 2 from ARMEEN 28 shown Polyurea and 150 files of ferchlorethylene 16 Hours is processed in the ball mill.

Example 22 A fabric made from a union of polyethylene j

Tereptttnalat and cotton is in a ratio of 30 s 50 is passed according to the calibration process through a mixture of 50 files of the red larbgtoffdiapersion used in Example 20 and 950 files perchlorethylene and then wiped with orphans and dried. Then the tissue is heated to 20O ⁴ I? For 2 minutes. received. The fabric is then rinsed in perchlorethylene and dried. The polyeate part of the

Tissue is stained red uniformly, the Feil made of cotton, on the other hand, is only about · dyed.

Example 23

Instead of the 10 parts of the dye dispersion used in Example 5, 10 parts of a dispersion are used which was obtained by using an oil from 10 parts of I ^^ - Dihydroiy - ^, ^ di (meth / 1amino) anthraohinone _v 163 parts of perehloroethylene and 5 parts of the polymer product, the vegetable. Example 9 of British patent specification 1 108 261 by esterification of polyhydrochloric acid with glycidyl methaerylate, condensation of the ester with a mixture of tinyltoluene and styrene and, finally, teresterification with p-aminobenzoic acid, which replaces the p-ffitrobenoic acid is used in an equivalent amount, was sucked, was processed in the Kugelatihle. 8this gives a uniform blue color

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109809/2030

Claims (1)

Fitent 1. Method of sun dyeing toe polymeric materials® dad ^ refr eekeiiiUMien & et « & mm das p ©! J» 8. »§ Material with a stable disentangledBisperalemvon © Sä» Dye is fine? ^ eiXehengröea · iß aine * meaais ^ iieB ffliisalejtoit «tosäie liquid ä $ sm emtfenat
pol ^ aere üateriel wilireat or wmfo der ■ it b 2 _β Terfata? · »Aoeh y _t ice cream Terfatoea Λ && ® di® Mi® * r8i © a by FiöÄetoffi? la das * Flme®i ^: eit .eiBen-'Bolyliarnetoff / ale Rittel. ' contains _f . di « -im -% eeetttlietie & - free -ven let vimd.aindettens »wii Harastof fgrugpea 'and aindestene' swai 'AUorl * ₉ .ükeayl »© der lll ^ p © ly®Barlew ^ p®a each with: B lolslenet © ffmt "niii emtliilt". κ f κιακς, o) Pt.-iK ©. H. lOit IWlrM & ft, SMiBMt OFiJGlNAL